Lead battery

ABSTRACT

Applying a grid which was obtained by punching or expanding a sheet comprising a pure lead (Pb:99.99 mass % or more) plate having a lead-tin alloy layer formed at least on one side of the pure lead plate to a positive electrode of a lead-acid battery, the problem that the pure lead grid shows bad charge acceptance characteristics after deep discharge can be solved, maintaining an excellent trickle life performance which a pure lead grid shows originally.

TECHNICAL FIELD

The present invention relates to a lead-acid battery.

BACKGROUND ART

The use of a lead-acid battery is classified into the trickle use (float use) in which said battery usually charges on fixed voltage and discharges as needed and the cycle use in which said battery charges and discharges repeatedly. The main cause of deterioration of the lead-acid battery in the former trickle use is the corrosion of a positive-electrode grid. This is because the alloy of the grain boundary used for a grid material is selectively corroded during charge.

Using the grid into which the pure lead sheet was processed was proposed by U.S. Pat. No. 3,862,861 as the provision.

Since the grain boundary of a pure lead is not clear, the above-mentioned problem due to the grain boundary does not occur and the excellent trickle life performance can be obtained. However, when a pure lead is used for a grid, in a cycle use, it has the defect which the capacity does not recover even if it charges, when deep discharge is performed especially.

As this provision, the method of making a lead-tin alloy instead of a pure lead into the shape of a sheet with rolling, and using the grid obtained by punching-processing or expanded processing was proposed by U.S. Pat. No. 5,120,620. Although the charge acceptance characteristics after deep charge can be improved by this method, since the metal used for said grid is a lead-tin alloy, a grain boundary exists, the corrosion of a positive-electrode grid advances in a trickle life, and there is a problem which is a short life compared with a pure lead grid.

DISCLOSURE OF INVENTION

A feature of this invention is that in a lead-acid battery which uses a grid which was manufactured by punching or expanding a rolled pure lead sheet, the pure lead sheet having a lead-tin alloy layer formed at least on one side of it is used for a positive electrode. By providing the layer containing Sn in the interface between the grid and a positive active material, this invention solves the problem that charge recovery characteristics in the pure lead grid is inferior after deep discharge, and provides a lead-acid battery maintaining an excellent trickle life performance which the pure lead shows originally.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the change of charging current during being charged under the charging acceptance characteristics test after deep discharge.

FIG. 2 is a graph showing the change in discharge capacity retention under the trickle (float) life test.

FIG. 3 is a graph showing a desirable range of the thickness ratio of the lead-tin alloy layer to the total thickness of the unified sheet, and relation between the tin content (mass %) of a lead-tin alloy layer.

FIG. 4 is a graph showing the results in which the performance of storage battery was reevaluated.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

This invention is explained at details based on an example below. This example describes a cylindrical valve-regulated lead-acid battery which wound spirally positive, negative electrode, and the separator, and was inserted into the cylindrical container using the soft property of a pure lead sheet.

In the valve-regulated lead-acid battery, the minimum quantity of electrolyte required for discharging is maintained on a glass separator by making the best use of excellent liquid maintainability with an absorptive glass mat separator (referred to as a glass separator) inserted into the section between positive and negative electrodes as a separator.

As described above, by making an electrolyte in starve condition, oxygen gas generated during charge can be easily penetrated and transferred to be reduced and absorbed on the negative electrode, eventually resulting in acquirement of excellent characteristics in oxygen cycle. More specifically, it is provided with functions as a maintenance-free lead-acid battery by repression of reduction in electrolyte due to oxygen cycle.

Moreover, the lead-acid battery according to the invention contains a feature as a non-spillable battery in which the electrolyte would not leak even if the lead-acid battery falls down, since an electrolyte is kept in starve condition, has been used in many fields recently.

Examples of the invention are hereinafter described with reference to the accompanying drawings.

Lead-Acid Battery A (Example of Invention)

By combining a lead-10 mass % Sn alloy plate thickness of which is 0.4 mm with a pure lead (99.99%) plate thickness of which is 10 mm, and rolling them, the combined sheet with a thickness of 0.6 mm was manufactured. By punching this sheet, the grid with a 5 mm×7 mm spaces for pasting was manufactured.

By applying the paste which is made by adding the dilute sulfuric acid to mixed powder of t-PbO, Pb₃O₄, and metallic Pb, to the above-mentioned grid, the positive-electrode was manufactured.

By applying the paste which is made by adding the dilute sulfuric acid to mixed powder of t-PbO and metallic Pb, to the grid which comprises a pure lead (lead:99.99 mass %) sheet, the negative-electrode was manufactured.

The plate thickness of both positive and negative-electrode plates is set to 0.9 mm.

These positive- and negative-electrode, and glass separators were combined, and the high pressure force (about 100 kPa) was applied to wind them spirally, and make an element (referred to as a configuration element which consists of combined positive- and negative-electrode plates, and a separator). This element was inserted into a cylindrical container with a diameter of 49 mm and a hight of 100 mm, and a cylindrical valve-regulated lead-acid battery which has 10 Ah discharge capacity (rated capacity) at 5 hr rate was made.

In addition, an object which is mainly composed of glass fibers with an average diameter of about 1 micrometer and into which 20 mass % of silica was mixed was used as a separator by being pressed under 20 kPa load into 0.8 mm thickness from about 0.9 mm thickness and about 91% porosity.

After filling container with about 115 g of electrolyte which was a solution to dissolve 25 g/l sodium sulfate into a dilute sulfuric acid and has its specific gravity 1.24 (at 20° C.), container formation was carried out. The container formation described herein indicates a formation under the condition where an unformed element is inserted into a container and electrolyte is poured in.

The battery manufactured by the above configuration and the method is set to A.

In order to demonstrate the excellent property in the lead-acid battery A of one example by this invention, the comparison test with conventional products were performed. The battery used for the comparison test in that case is shown concretely.

Lead-Acid Battery B (Comparison Example)

The grid manufactured by the same method as the above was used for the positive-electrode from the sheet with a thickness of 0.6 mm which carried out rolling processing of the pure lead (Pb:99.99 mass %) plate, and the lead-acid battery B as well as the aforementioned lead-acid battery A was manufactured for other configurations.

Lead-Acid Battery C (Comparison Example)

The grid manufactured by the same method as the above was used for the positive-electrode from the sheet with a thickness of 0.6 mm which carried out rolling processing of the 99.0 mass % lead-1.0 mass % tin alloy plate, and the lead-acid battery C as well as the aforementioned lead-acid battery A was manufactured for other configurations.

About three kinds of above-mentioned batteries, the comparative study of the charge acceptance characteristics after deep discharge and the trickle life performance was performed. Those results are shown below.

The Charge Acceptance Characteristics after Deep Discharge Test condition

After discharging the above-mentioned battery to final voltage 1.7 V with the current of 2 A, moreover, 100 ohm resistance was connected for 14 days, and the battery was made into the deep discharge condition. Then, after leaving the battery whose resistance was removed under 0° C. environment for 16 hours, constant voltage charge of 2.4 V (limit current 50 A) was performed for 10 minutes, and change of the charging current at this time was observed.

Test Result

A test result is shown in FIG. 1.

In the lead-acid battery B using a pure lead, the charging current was kept 0 A during the charge for 10 minutes, and it was hardly charged, so the charge acceptance characteristics was bad. On the other hand, in the lead-acid battery A according to the invention and the lead-acid battery C using only a lead-tin alloy, the charging current flowed and their charge acceptance characteristics were good.

As a result of the test, it was found that presence of tin in the positive-electrode grid is effective to improve the charge characteristics after deep charge. Especially, although the positive-electrode grid of the lead-acid battery A according to the invention has few tin contents compared with that of the lead-acid battery C, since tin intensively exists in the portion in contact with positive active material, it can be said that existence of the tin acted more effectively.

Trickle (Float) Life Test Test Condition

The above-mentioned battery was constantly at trickle-charge voltage 2.275 V in the gaseous phase with an environmental temperature of 60° C., it was taken out every month, and the capacity test was performed at discharge current 10 A (final voltage 1.0 V).

Test Results

The test results are shown in FIG. 2.

Although the capacity in the lead-acid battery C was less than 50% of initial capacity after 5 months, 50% or more of initial capacity was maintained even after 10 months in the lead-acid battery A and the lead-acid battery B using pure lead.

Although the grain boundary corrosion which is the feature of an alloy grid was advancing considerably in the Lead-acid battery C when the battery was disassembled after the test and the positive-electrode was investigated, little grain boundary corrosion of a grid was observed in the Lead-acid battery A and Lead-acid battery B.

As shown in these test results, since the positive-electrode grid of the Lead-acid battery A comprises a combined sheet which was created by combining a pure lead (Pb:99.99 mass %) plate with the lead-10 mass % tin alloy plate and rolling them, unlike an grid which was created by rolling only a lead-tin alloy, tin exists intensively on a surface section with which an active material comes in contact, and much pure lead exists in other sections, it is assumed that the effect of the pure lead in a trickle life was obtained.

Lead-acid batteries D-1 to K-5

In the configuration of the Lead-acid battery A, an appropriate range of thickness of a lead-tin alloy layer which is combined with a pure lead sheet and the content of a tin is described on the test results.

Effect of Lead-Tin Alloy Layer Thickness and Tin Content on Performance Lead-Acid Battery Test Condition

In order to investigate the effect of the ratio of the lead-tin alloy layer thickness to the total thickness of the combined sheet and the content of tin per weight of the combined sheet, by rolling lead-tin alloy plates which contain 0.3 mass %, 0.5 mass %, 1 mass %, 10 mass %, 20 mass %, 25 mass %, 30 mass %, 40 mass %, 45 mass %, and 50 mass % as a tin content, sheet materials (0.03 mm, 0.05 mm, 0.11 mm, 0.42 mm, 2.5 mm, 4.3 mm, 6.7 mm, and 8.2 mm in thickness,) were manufactured. Moreover, by combining the lead-tin alloy sheet material with a pure lead (Pb: 99.99 mass %) plate the thickness of which is 10 mm and continuing to roll the until the thickness reaches to 0.6 mm, combined sheets comprising pure lead alloy plate and lead-tin alloy plate were manufactured.

Next, the sheets were punched to manufacture positive-electrode grids having 5 mm×7 mm space for pasting, which were used for positive electrode to manufacture 29 kinds of lead-acid batteries (lead-acid batteries D-1 to K-5). In these batteries, the same configuration as that of the lead-acid battery A was applied to those of these lead-acid batteries except for that of the positive-electrode grid.

X(%) and Y(%) are shown in Table 1 in the positive-electrode grid used for the lead-acid batteries D-1 to K-5, wherein X(%) is a ratio of the lead-tin alloy layer thickness to a total sheet thickness and Y(%) is a ratio of Sn content to the lead-tin alloy layer mass. TABLE 1 Thickness ratio of alloy Kind of lead-acid layer Sn content of alloy layer battery X(%) Y(mass %) D-1 0.3 0.5 D-2 0.3 10 D-3 0.3 50 E-1 0.5 0.3 E-2 0.5 0.5 E-3 0.5 10 E-4 0.5 45 E-5 0.5 50 F 1 10 G-1 4 0.3 G-2 4 0.5 G-3 4 1 G-4 4 10 G-5 4 20 G-6 4 40 G-7 4 45 G-8 4 50 H 20 10 I-1 30 0.5 I-2 30 10 I-3 30 20 I-4 30 30 I-5 30 40 J 40 10 K-1 45 0.3 K-2 45 0.5 K-3 45 10 K-4 45 25 K-5 45 40

These 29 kinds of lead-acid batteries underwent charge acceptance characteristics test after deep discharge and trickle life test. The above-mentioned tests were conducted under the same conditions for the comparison test for the afore-mentioned lead-acid batteries.

The test results are shown hereinafter. TABLE 2 Kind of Test results of charge acceptance lead-acid characteristics after deep Test results of trickle life battery discharge performance D-1 x ∘ D-2 x ∘ D-3 x ∘ E-1 x ∘ E-2 ∘ ∘ E-3 ∘ ∘ E-4 ∘ ∘ E-5 ∘ x F ∘ ∘ G-1 x ∘ G-2 ∘ ∘ G-3 ∘ ∘ G-4 ∘ ∘ G-5 ∘ ∘ G-6 ∘ ∘ G-7 ∘ ∘ G-8 ∘ x H ∘ ∘ I-1 ∘ ∘ I-2 ∘ ∘ I-3 ∘ ∘ I-4 ∘ ∘ I-5 ∘ x J ∘ ∘ K-1 ∘ x K-2 ∘ x K-3 ∘ x K-4 ∘ x K-5 ∘ x

In table 2, the test results of charge acceptance characteristics test after deep discharge and trickle life performance test were evaluated in accordance with the following criteria. As a result, the case where the charging current was not 0 A from the test start to the end (that is, charge can be accepted) was judged to be “good”.

(Test Results of Charge Acceptance Characteristics after Deep Charge)

-   -   =>o: where charge acceptance characteristics is in good         condition     -   =>x: where charge acceptance characteristics is not in good         condition

(Test Results of Trickle Life Performance)

-   -   =>o: where discharge capacity after 10 months is more than 50%         of the initial capacity     -   =>x: where discharge capacity after 10 months is less than 50%         of the initial capacity

Next, in FIG. 3 where the above-mentioned “X” values are indicated along the X axis and “Y” values are indicated along the Y axis, “o” mark was made on the test results of both charge acceptance characteristics test and trickle life test are acceptable and “X” mark was made on the test results where either result of the above-mentioned tests are unacceptable.

It was found that the lead-acid batteries which are located on the range of 0.5≦X≦40 and 0.5≦Y≦−0.625X+50 have an excellent trickle life performance and favorable charge acceptance characteristics after deep charge.

Moreover, the above-mentioned trickle life performance test results were reevaluated on the following criteria.

-   -   =>o: where discharge capacity after 10 months under trickle         performance test is more than 70% of the initial capacity     -   =>x: where discharge capacity after 10 months under trickle         performance test is less than 70% of the initial capacity

The above-mentioned results are shown in Table 3. TABLE 3 Kind of lead-acid batteries Test results of trickle life performance D-1 ∘ D-2 ∘ D-3 x E-1 ∘ E-2 ∘ E-3 ∘ E-4 ∘ E-5 x F ∘ G-1 ∘ G-2 ∘ G-3 ∘ G-4 ∘ G-5 ∘ G-6 ∘ G-7 ∘ G-8 x H ∘ I-1 ∘ I-2 ∘ I-3 ∘ I-4 ∘ I-5 x J x K-1 x K-2 x K-3 x K-4 x K-5 x

Based on the above-mentioned reevaluated test results, “o” mark was made on the test results of both charge acceptance characteristics test and trickle life test are acceptable and “x” mark was made on the test results where either result of the above-mentioned tests are unacceptable, in FIG. 4.

It was found that the lead-acid batteries which are located on the range of 0.5≦X≦40 and 0.5≦Y≦−0.625X+50 in FIG. 4, have an excellent trickle life performance and favorable charge acceptance characteristics after deep charge.

It was found that the charge acceptance characteristics after deep charge in the range of X<0.5 and Y<0.5 in FIG. 3 are poor. This is because a lead-tin alloy layer was thin or Sn content in a lead-tin alloy layer was little in the above-mentioned range, which could not sufficiently resolve the problem with the pure lead positive grid which is inferior in charge acceptance characteristics.

In addition, in the range of X>50 and Y>−0.625 X+50, the trickle charge characteristics becomes inferior. This is because in the above-mentioned range, the lead-tin alloy thickness and Sn content were excessive, resulting in development of grain boundary corrosion, which caused a conductive path (non-corrosion section) remaining in the positive grid which would affect a trickle life performance to be narrowed.

Accordingly, with respect to the ratio “X” of the lead-tin alloy layer thickness to the total sheet thickness, to improve the trickle life performance and charge acceptance characteristics after deep charge, it is desirable that the ratio is 0.5≦X≦40, or moreover 0.5≦X≦30. From the same viewpoints, with respect to the Sn content “Y” per lead-tin alloy layer mass, it is desirable that the content is 0.5≦Y≦−0.625X+50. In addition, it is the most optimal that said X and Y are located in the range of 0.5≦X≦40 (moreover, 0.5≦X≦30) and 0.5≦Y≦−0.625X+50.

As mentioned above, by applying a grid, which is produced from a combined sheet obtained by combining a lead-tin alloy plate with a pure lead (99.99 mass % or more) plate and rolling them, to positive electrode, a valve-regulated lead-acid battery which has excellent trickle life performance without problems in charge acceptance characteristics after deep charge can be got.

In the above-mentioned examples, although a lead-tin alloy containing 0.5 to 50 mass % Sn content is used as a lead-tin alloy, since existence of tin contributes to the improvement of charge acceptance characteristics after deep charge, it is preferable to use a lead alloy containing a tin and other metal materials such as a lead-tin-calcium alloy, etc. In this case, it is necessary that tin content “Y” (mass %) satisfies the formula for 0.5≦Y≦−0.625X+50.

In the above-mentioned examples, the effect of the cylindrical valve-regulated lead-acid battery according to the invention was described. However, the same effect can be provided with not only cylindrical valve-regulated lead-acid battery, but also so-called flooded type lead-acid battery which is applied similar positive plate, because the effect is originated from positive grid.

Moreover, in the above-mentioned examples, although a lead-tin alloy layer is rolled and combined with a layer consisting of a pure lead plate, as the method to provide a lead-tin alloy layer on a surface of a pure lead plate, a chemical vapor deposition method, physical vapor deposition methods, a diffusion penetration method or electrochemical plating methods, etc. can be used. However, in these methods, the method by rolled processing is the simplest, the most economic and excellent in mass production.

INDUSTRIAL APPLICABILITY

The lead-acid batteries which have an excellent trickle life performance and no problems in charge acceptance characteristics after deep charge are able to be got by using a grid obtained by punching or expanding a sheet comprising a lead-tin alloy layer on at least one side of surface of a pure lead plate, and making, in addition, the thickness of lead-tin alloy layer (a ratio of the thickness of the layer to the total sheet thickness) and/or the content of Sn proper value.

Moreover, a combined sheet obtained by combing a lead-tin alloy plate with a pure lead plate and rolling them can be used for the above-mentioned positive grid. The invention demonstrates an extremely high industrial value because the production method according to the invention is simple and economy, moreover, excellent in mass production. 

1. A lead-acid battery comprising: a positive electrode, a negative electrode and a separator lying between said positive electrode and said negative electrode; wherein, as a grid of said positive electrode, a grid which is obtained by punching or expanding a sheet comprising a lead-tin alloy layer on at least one side of surface of a pure lead (Pb:99.99 mass % or more) plate is used.
 2. The lead-acid battery according to claim 1, wherein a ratio X(%) of said lead-tin alloy layer thickness to a total sheet thickness, satisfies the formula for 0.5≦X≦40.
 3. The lead-acid battery according to claim 1, wherein a ratio X(%) of said lead-tin alloy layer thickness to a total sheet thickness, satisfies the formula for 0.5≦X≦30.
 4. The lead-acid battery according to claim 1, wherein a ratio Y(mass %) of Sn content to said lead-tin alloy layer mass and a ratio X(%) of a lead-tin alloy layer thickness to a total sheet thickness satisfy the formula for 0.5≦Y≦−0.625X+50.
 5. The lead-acid battery according to claim 2, wherein a ratio Y (mass %) of Sn content to lead-tin alloy layer mass, satisfies the formula for 0.5≦Y≦−0.625X+50.
 6. The lead-acid battery according to claim 3, wherein a ratio Y (mass %) of Sn content to lead-tin alloy layer mass, satisfies the formula for 0.5≦Y≦−0.625X+50.
 7. The lead-acid battery according to claim 1, wherein said lead-tin alloy layer is combined into a layer comprising said pure lead plate by rolling process. 